Process for making chlorinated hydrocarbons.



F. W. MANN & M. L. CHAPPELL. PROCESS FOR MAKING CHLORINATEDHYDROCARBONS. APPLICATION FILED APR. 16. 1915 1,183,094, v PatentedMay16, 1916.

v 9 i3 L $1 Rp F \I N N Q 1 5 Y, 1 33 g Q N w UNITED STATES PATENTOFFICE.

rnnnnmcx WILLIA-MVMANNEAND mVIN LEE CHAPCPELL, or BERKELEY, cALI-ronNIA, AssIeNons-To STANDARD OIL COMPANY, or RICHMOND, CALIFORNIA,

A CORPORATION OF CALIFORNIA.

To all wkom z't may concern Be it known that WQVFREDERICK WILLIAM MANNand MARVIN LEE CHAPPELL, citizens of the United States, residing atBerkeley, in the county of Alameda and State of California, haveinvented certain new. and useful Improvements in Processes for MakingChlorinated Hydrocarbons, of which the following is a specification.

This invention relates to the production and separation of chlorinatedhydrocarbons, and particularly to their production and separation fromdistillates of crude petroleun'i.

In carrying out the process, petroleum distillates are used whichcontain a high percentage of aromatic and unsaturated hydrocarbons, andwhich are acted upon by sulfuryl chlorid, forming the correspondingchlorin compounds, such, for example, as-

carbon oils by dissolving them in liquefied sulfur dioxid at I asultable temperature,

' which for the best results is one below 32 degress Fahr.

From the above it will be seen that-for a brief statement of the natureof the process in its essentials, it may be said-to consist in treatingthe distillates from crude petroleum with sulfuryl chlorid dissolved inan excess of liquefied sulfur dioxid at a temperature below 32degreesFahr. This process is lparticularly applicable for obtaining ch orinatedhydrocarbons from California petroleum distillates or similar pertoleumdistillates, which carry from 1 to 5% olefinic hydrocarbons, such asoctylene, nonylene,

decyleneand the like, and from 10 to25% Y aromatic hydrocarbons such, asxylene,

I Speciflcation of Letters Patent. Application filed April 16, 1915.Serial No. 21,668.

'leu'm distillate to be treated. Petroleum disare separated rnocnss r03MAKING c ILonINA'rEn HYDROCARCBONS.

Patented May 16, 1916.

mesitylene, cymene, pseudo-cumene and the like. The chemical compositionof the petroleum distillate to be treated is determined and thenecessary amount of chlorin calculated. This calculated amount ofchlorin is added to the liquefied sulfur dioxid forming sulfuryl chloriddissolved in an excess of liquid sulfur dioxid. The amount of liquIdsulfur dioxid necessary also depends upon the chemical composition ofthe petrotillates containing a high percentage of aromatlc and olefinichydrocarbons may require as much as two volumesof liquid sulfur dioxidand 5% by weight chlorin. For example, a petroleum distillate whichcontains 3% olefinic hydrocarbons and 20% aromatic hydrocarbons,requires of one pound of liquid chlorin dissolved in 21 pounds of liquidsulfur dioxid, for each gallon of distillate. We do not confineourselves to these proportions since we could use 'of a pound of chlorindissolved in 15 or 24 lbs. of liquid sulfur dioxid.

We are aware that the art of making chlorinated hydrocarbons by theaction of sulfuryl chlorid on coal-ear distillates is well known. Thenovelty of our invention, however, consists in the application of sulfuryl chlorid in the presence of an excess of sulfur dioxid, andapplying the same to petroleum distillates containing a high percentageof olefinic and aromatic hydrocarbons, which results in the formationand separation of chlorinated hydrocarbons. By the action of thesulfur'yl chlorid we'*90 form chlorinated olefinic and aromatichydrocarbons, such as dichlor-octane 0 11 01 dichlor nonane C H Cldichlor decane O H Ch, chlor-xylene C H CI, chlormesitylene C H Cl,chlor-cymene O H Cl, chlor-pseudo-cumene C H CI and the like. Thefunction of the large excess of liquid sulfur dioxid is to dissolve andseparate the chlorinated hydrocarbons by the action stated' The processmore particularly stated is as follows:,The oil to be treated is chargedinto a tank. Liquefied sulfur dioxid containing chlorin is added fromthe top, preferably by being sprayed. For example, onehalf to twovolumes of the liquefied sulfur dioxid containing the predeterminedpercentage of chlorin are used for each volume or the oil tobe treated.This treating mixture is made by adding the predetermined amount ofchlorill, say 1% to by weight, to the liquid sulfur dioxid, underpressure, say 0175 to 100 pounds. The suliuryl chlorid thus formed isdissolved in an excess of liquid sulfur dioxid. After introducing thisheat interchanger used in the manufacture of ticularly 1 adapted.

second treating -miXture, the contents of the tank are agitated, thisbeing best done by means of a vacuum pump, communicating with the top ofthe tank, the vacuum causing some of the liquefied sulfur dioxidto'vaporize, thus producing sulficient agitatiomandat the same timelowering the temperature to the desired point. The sulfur dioxid,which-is thus 'va-' porized, is condensed and recovered. the oil undertreatment has had sufiicie'nt agitation and the reaction. is finished,the" vacuum pump is stopped and the chlorinated hydrocarbons dissolvedin the liquefied sulfur dioxid settle to the bottom. In this way formed.The bottom layer oil is drawn off through a where it partially coolsdown theincoming charge of oil which at two layers are of the treatedthis time is being delivered to a second treat-- ing tank, a companionofthe first tank. From the heat interchanger the bottom layer enters astill in which the remaining sulfur dioxid is distilled ofi, condensedand conducted to a storage tank for use again. The

separated chlorinated aromatic and chlorun into a st ll, in which thesulfur dioxld is distilled oil, condensed and conductedto the storagetankfor use again. In some cases, the top layer oil thus-obtained is notfor-[the market, and it is necessary to treat it with a small amount orsufficiently pure sulfuric acid.

The process will be more understocd by reference to the accompanyingdrawing in which the. figure illustrates one form of an apparatusadapted for carrying it out.

1 and 2 are treating tanks.

3 is the oil supply pipe controlled by a valve4.- .j r

5 is a feed pump-with which the supply pipe 3 communicates,and-6is thecharging pipe, which: leads'into thejitreating tank 1 by a branch 7controlled Zia valves, leads iiltothe charging ta 9 controlled-thy.avalve 10.

11 is a storage .tank fcr the mixture bf.

' sulfuryl chlorid and liquefied sulfur dioxid.

' From this stora 4 leads a delivery pipe 12, controlled byavalve13,said pipe ter- When ,1 and 2 issues a pipe 'pipe leading to a pipe 37with a valve 38 leads to a still 39 the into the treating I --11 ischarged 2,,hy a branch pipes 21 ,cea

minating in a branch 14 controlled by a valve 15, and entering the tank1, its extremity being fitted with a spraying device 16. From the pipe12, a similar branch 17' controlled by a valve 18, enters the tank 2 andis fitted with a spraying device 19.

20 is a compressor which on its suction side has a pipe 21, with acontrolling valve 22. With this suction pipe a pipe 23, which, by abranch 24, having a valve 25, communicates with the top of the tank 1,and by a branch 26, having a valve 27, communicates with the top of thetank 2.

' From the pressure side of the compressor 20 leads a pipe 28, which iscoiled through a condenser box 29, and then enters the storage tank 11.From the bottom of the tanks 30, from which a pipe 31, with a valve 32,leads to a heat inter changer shell 33 in which the charging pipe 6 iscoiled. From thisheat interchanger shell issues a pipe 34 with a valve35, said pump 36,. from which a in which is a. steam coil 40. From thestill 39 leads a pipe 41, having a valve 42, to a second still43,'fitted with a steam coil 44.

From the still 43 issues a valve controlled discharge pipe 45.

From the bottom leading to a pump 48 from which a pipe 49 extends to andcommunicates with a heatinterchanger shell50' in which the delivery p1pe12 is coiled. From this shell 50 leads a pipe 51 having a valve 52, saidpipe entering a still 53, in which is a steam coil 54. This still isconnected by a pipe 55, having a valve 56, with a still 57 in which is asteam coil 58. The still 57 has a valve con trolled discharge pipe 59.

The suction ipe 21 of the compressor 20 connects with tie still 43 by abranch pipe 60 having a valve 61, and it connects with the still 57 by abranch pipe 62 having 'a valve 63.

' From the pressure pipe 28 of comki pressor 20 leads a pipe 64, whichconnects with the still-39 by a branch pipe 65 having a valve 66, and itconnects with the still 53 by a branch pipe 67 having a. valve 68.

Thecourses of the several fluids through the apparatus are indicated bythe arrows. The method carried out in this apparatus is, in detail, astollowsz supplied through pipe 3, is, by means of the pump 5, p1pef6 andbranch pipe 7, charged with liquefied sulfur dioxid containing 1% to.5%, by weight, of chlorin.

This mixture is introduced into the tank 1 through the pipe 12, branchpipe 14 and spraying device 16. Then the compressor 20 i is started,which taking suction through 21 is connected of the tanks 1 and 2'issues a pipe 46 having a valve 47, said pipe Petroleum distillate,

tank 1. The storage tank and 23 and branch pipe 24, reduces 1 thepressure in the tank 1,"and cauxs a porpassed through the pipe 28 coiledin the condenser 29, through which a constant flow of cold water ismamtained. In-this coil under suflicient pressure it becomes llq uefiedand flows into the storage tank 11. he heat of compression isneutralized by the cold water in the condenser. When the treated oil inthe tank 1 has had sufiicient agitation and has reached the desiredtemperature, the

compressor 20 is stop ed and the valve 25 at the branch 24 into t e tankis closed. The mixture in said tank separates into two layers. Thebottom layer, consisting of chlorinated aromatic oils, and chlorinatedunsaturated hydrocarbons held in solution b the liquid sulfur dioxid, isdrawn 0 through the pipes 30 and 31, into. the heat exchanger shell 33,and at the same time the other treating tank-2 is charged by the pump 5with fresh distillate for the next treatment. Thus in the charging pipe6 and the shell 33 there is an exchange of heat be-' tween the incomindistillate and the outgoing chlorinated ydrocarbons and liquid sulfurdioxid. After this exchange of heat,

- partial vacuum produced throu the chlorinated liquid sulfur dioxidmixture is delivered. by the pi e 34.to the pump 36, by which it isfo'rced through the pipe 37 into the still 39. Inthis still, by means ofthe steam coil 40, the temperature is raised sufiiciently to va orizenearly all the liquid sulfur dioxid. he vaporized sulfur dioxid passesfrom the still 39, through the pipes 65 and 64 into the compressor pipe28, in the condensing coil of which it is under suflicient pressure tobeliquefied, and as a liquid it then runs into the storage tank 11.

In order to separate morecompletely the chlorinated bottom layer oilfrom the sulfur dioxid, it is drawn from the still 39, through the'pipe41 into the still'43, which is heated bythe steam coil 44 and is ke tunder a pressor suction pipe 21 and the ranch pipe 60. The top layer oilin the tank 1, is next taken off through the pipe 46, and by meansof thepump 48 is assed through the ipe 49 into the heat exc anger shell 50, inw ich i it part1 cools down the liquid sulfur dioxid s'ulfury chloridmixture, which is, at the 1 same time, passing through the coil pipe 12on its 'way to the second treating tank2 tobe delivered therein throughthe spraying device 19; From the exchanger shell 50,the topla er oiloverflowsthrough the pipe 51 into the still 53, wherein, under the heatfrom the steam coil 54, most of the remain order to free more complete yoil from sulfur dioxid, it is drawn from thepipe 55 into the still 57,

the coming dioxid seemed-sates itsa vapor passin through'pipes 67 and 64enter pipe 28 and is condensed in the coil of said ipe in the water box29, and thence as a quid runs into the stem thistop layer still 53through the which is heated by the steam coil 58 and is" kept underpartial vacuum through the pipes 62 and 21. From the still 57"the oilruns to a storage tank through the pipe 59, while the contents theirdestination throughth pipe 49.

If necessary the oil from still 5,? is treated finally with a smallamount of -sulfuric acid, washed and neutralized acording; to the wellknown methods. y

The separated A chlorinated hydrocarbon oils are used in the dyeindustry; for-fire extinguishers, and in the manufacture of variouschemicals. The oil from which the chlorinated hydrocarbons have been're-. moved, that is, the non-chlorinated saturated hydrocarbons, can beused-for lamp oils, or for otherpurposes for which they ma be adapted.

- i e claim:-

L-That step. in the process consists in treating petroleum distillateswith sulfuryl "chlorid in the presence of liquefied sulfur dioxid.

2. .That step in the recess of making chlorinated hydrocarbons whichconsists in treating petroleum .distillates .with sulfuryl chlorid -1nthedioxid at temperatures below 32 degrees Fahr. The process of makingchlorinated hydrocarbons, which consists 1n first treating petroleum,distillate's with sulfuryl chlo ri in the presence of liquefied sulfurdioxid to chlorinate the unsaturated and aromatic hydrocarbons present.and to dissolve said chlorinated products; and then separatingthe-resultant liquids. a

4; They process of making chlorinated hydrocarbons, which consists infirst treatin petroleum distillates withsulfuryl chlori m the presenceof liquefied sulfur dioxid, at temperatures below 32 degrees Fahr., tochlorinate the unsaturated and. aromatic hydrocarbon present and todissolve said chlorinated products; andfthen separating the resultantliquids. I

5. The process of making ri 1n thepre'sence of liquefied sulfur dioxidto chlorinate the unsaturated and aromatic hydrocarbons present and todissolve said chlorinated products; vaporizing suflicient' of the sulfurdioxid, during'said treatment, to produce a temperature of below 32'de-- tank 11., 11170 of the still.43 pass to presence of liquid sulfur rchlorinated hydrocarbons, which consists 1n first treatinpetroleumdistillates with sulfuryl chlo- I" grees Fahr. and finallyseparating the re-= sultant liquids.

' 6. The process of making chlorinated hydrocarbons, which consists infirst treat ing petroleum distillates with sulfuryl ch10 rid in thepresence of liquefied sulfur dioxid to chlorinate the unsaturated andaromatic hydrocarbons present and to dissolve said chlorinated products;vaporizing suiiicient of the sulfur dioxid, during said treatment, toproduce a'temperature of below 32 degrees Fahrz; separating'theresultant liquids; and finally separating the remaining sulfur dioxidfrom each of said resultant liquids.

7. The process of making chlorinated hydrocarbons which consists infirst sepa rately treating petroleum distillates in successive charges,with sulfuryl chlorid in the presenoe of sulfur dioxid,'at temperaturesasse ses below 32'degrees Fahu, to ehloriiiaee the unsaturated andaromatic hydroearbonspresent and to dissolve said chlorinated products;then separating the resultant liquids, and, in said separation,exchanging the heat of the liquids of one charge, with the incoming.petroleum distillates, and the chlorinated sulfur dioxid treatingmixture of the succeeding charge; and finally separating; the sulfurdioxid from each of said resultant liquids.

in testimony whereof we have signed our names to this specification inthe presence of two subsoribi witnesses. FREDERI K WILLIAM MANN}. MARVINLEE CHAPPELL. Witnesses:

WM; F. 300113, D, B. Rronmus.

